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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Concordance cosmology?

ABSTRACT We propose a new intuitive metric for evaluating the tension between two experiments, and apply it to several data sets. While our metric is non-optimal, if evidence of tension is detected, this evidence is robust and easy to interpret. Assuming a flat Lambda cold dark matter (ΛCDM) cosmological model, we find that there is a modest 2.2σ tension between the Dark Energy Survey (DES) Year 1 results and the Planck measurements of the cosmic microwave background. This tension is driven by the difference between the amount of structure observed in the late-time Universe and that predicted from fitting the Planck data, and appears to be unrelated to the tension between Planck and local estimates of the Hubble rate. In particular, combining DES, baryon acoustic oscillations, big bang nucleosynthesis, and supernovae measurements recover a Hubble constant and sound horizon consistent with Planck, and in tension with local distance–ladder measurements. If the tension between these various data sets persists, it is likely that reconciling all current data will require breaking the flat ΛCDM model in at least two different ways: one involving new physics in the early Universe, and one involving new late-time Universe physics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Blue Rock CropSpanPV - Low Cost Racking for Agricultural Solar Photovoltaics

In this work, a total of four solar panel layouts, applied to Agrivoltaics, are investigated. This study presents two hypotheses: 1. Prefabrication - Lower total cost can be achieved by constructing a pre-assembled, pre-wired solar array in a factory, with automation, then rapidly deploying it in the field. 2. Tension Structures - Using tension structures in a way to suspend an overhead solar array also reduces costs when compared to conventional support methods. Designs are presented for frames to hold the panels. Configurations are advanced to connect the frames into arrays. Supports and foundations to hold the arrays in the desired layout are calculated, selected and presented. Cost models are prepared for the four layouts, which include definition of the business enterprise, the manufacturing operation, and the required facility for production at scale. Cost models include, detail material and task/labor take-offs for both manufacturing and installation. Comparisons with conventional system adapted to Agrivoltaics reveal that the two hypotheses do not hold true. A prefabricated array requires additional material that is not needed in the base system and the cost of this additional material is not outweighed by the cost savings of reduced field installation. The cost of wire rope for a tension structure does result in an economy of material, however, the cost of end connections and tensioning devices adds significantly to the cost of the overall tension structure. Foundation loads with tension structures, especially the large wind uplift seen with a fixed tilt solar array, impose significant constraints and high costs. The following conclusions are recommended for further consideration: 1. Best Case Agrivoltaic Configuration - The best value/lowest cost configuration for agrivoltaics is the installation of solar panels mounted on a single axis tracker in either a 2-in-portrait or 2-in landscape arrangement. This is useful for grazing lands and for staple crops which require high light levels. These applications represent the vast majority of the potential agrivoltaic market. Important elements in this configuration are the specific geometric layout coordinated with the various field operations and a control system linked between the farm equipment and single axis tracker. The control system is to monitor location and orientation, then actively tilt the solar panels or brake the field equipment to provide clearance and avoid collisions. 2. Long Span Applications - The use of tension structures for an overhead fixed tilt array is beneficial where long spans are a necessity, especially where the base support in the project location has consolidated rock near the surface or some other solid structure. One application is spanning wide irrigation canals. Another may be as an installation at the top deck of parking structures. 3. Direct Ground Mount Configuration – Having skids at the base of a pre-fabricated array that extend when the array is deployed, could be a successful design. This could be a useful strategy for dense, flat, ground-mount configurations like that employed by a couple of successful commercial operations (5G Maverick and Erthos). Arrays would be orientated north and south, deployed very low on prepared grade. Arrays would be aligned closely next to each other and anchored with small ground screws or simply with ballast. This same product arrangement could be very useful for rapid deployment and set-up of solar arrays for temporary deployments, disaster response and the military operations

14 SOLAR ENERGY↗
DOE OSTI2026

SPT-3G D1: Axion early dark energy with CMB experiments and DESI observations

We present the most up-to-date constraints on axion early dark energy (AEDE) from cosmic microwave background (CMB) and baryon acoustic oscillation (BAO) measurements. In particular, we assess the impact of data from ground-based CMB experiments, the South Pole Telescope (SPT) and the Atacama Cosmology Telescope (ACT)—both with and without Planck—on constraints on AEDE. We also highlight the impact that BAO information from the Dark Energy Spectroscopic Instrument (DESI) has on these constraints. From CMB data alone, we do not find statistically significant evidence for the presence of AEDE, and we find only moderate reduction in the Hubble tension. From the latest SPT data alone, we find the maximal fractional contribution of AEDE to the cosmic energy budget is f EDE < 0.12 at 95% confidence level (CL), and the Hubble tension between the SPT and Supernovae, H0, for the Equation of State of Dark Energy (SH0ES) results is reduced to the 2.3 σ level. When combining the latest SPT, ACT, and Planck datasets, we find f EDE < 0.070 at 95% CL and the Hubble tension at the 3.6 σ level. In contrast, adding DESI data to the CMB datasets results in mild preference for AEDE and, in some cases, non-negligible reduction in the Hubble tension. From SPT + DESI , we find f EDE = 0.08 1 - 0.052 + 0.037 at 68% CL, and the Hubble tension reduces to 1.5 σ . From the combination of DESI with all three CMB experiments, we get f EDE = 0.05 5 - 0.047 + 0.024 at 68% CL and a weak preference for AEDE over Λ CDM . This data combination, in turn, reduces the Hubble tension to 2.6 σ . We highlight that this shift in parameters when adding the DESI dataset is a manifestation of the discrepancy currently present between DESI and CMB experiments in the concordance model Λ CDM .

Khalife, A. R. [Paris, Inst. Astrophys.] (ORCID:00↗
DOE OSTI2022

Detecting cosmic strings with lensed fast radio bursts

Correlated red noise recently reported from pulsar timing observations may be an indication of stochastic gravitational waves emitted by cosmic strings that formed during a primordial phase transition near the grand unification energy scale. Unfortunately, known probes of cosmic strings, namely the cosmic microwave background anisotropies and string lensing of extragalactic galaxies, are not sensitive enough for low dimensionless string tensions of Gμc -2 = 10 -10 – 10 -7 (where the tension μ is the string energy per unit length) that are needed to explain this putative signal. We show that strong gravitational lensing of fast radio bursts (FRBs) by cosmic strings is a potentially unambiguous avenue to probe that range of string tension values. The image pair of string lensing are expected to have identical magnification factor and parity, and have a typical time delay of ~10 2 (Gμc -2 /10 -8 ) 2 s. Here, the unique spectral fingerprint of each FRB, as well as the possibility to detect correlations in the time series of the electric field of the radio waves, will enable verification of the string lensing interpretation. Very-long-baseline interferometry observations can spatially resolve the image pair and provide a lower bound on the string tension based on the image separation. We calculate the FRB lensing rate as a function of the FRB detection number for several different models of the FRB redshift distribution. We find that a survey detecting ~10 5 FRBs, in line with estimates for the detection rate of the forthcoming survey CHORD, can uncover a strong lensing event for a string tension of Gμc -2 ≃ 10 -7 . Larger FRB surveys, such as Phase 2 of the Square Kilometre Array, have the potential to significantly improve the sensitivity on the string tension to Gμc -2 ≃ 10 -9 .

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Virtual texture analysis to understand microstructure effects on deformation twinning and detwinning behavior in BCC metals

Understanding and predicting deformation twinning contributions to plastic deformation in BCC metals has been a long-standing challenge due to the interplay with dislocation slip and non-Schmid effects that render an asymmetry under tension and compression. This paper uses molecular dynamics simulations to understand the effect of unloading and grain orientation on deformation twinning in a nanocrystalline Fe (nc-Fe) system as a model BCC metal. The nc-Fe system is loaded under uniaxial stress tension and compression to understand the effect of grain orientation (Schmid effects) on deformation twinning behavior and the tension/compression asymmetry (non-Schmid effects). A new virtual texture analysis “VirTex” tool is used to understand the role of grain orientation on the nucleation of twins and their contributions to the observed stress–strain response. For certain grain orientations, the twinnability is observed to be different in tension and compression. In addition, the flow stress accommodation from twins in certain grains is observed to be different in tension and compression and different from that for the grains. Subsequent unloading leads to detwinning in the deformed microstructures, where the extent of detwinning depends on the strain from which the system is unloaded and on the morphology of the twin. Lastly, the simulations are carried out to analyze the role of the Schmid factor on the twinnability and asymmetry in tension and compression.

Kannan, Aadhithyan [University of Connecticut, Sto↗
DOE OSTI2024

Early dark energy constraints with late-time expansion marginalization

Abstract Early dark energy (EDE) is an extension to the ΛCDM model that includes an additional energy density contribution near recombination. The model was proposed to reduce the tension between the measurements of the Hubble constantH 0 from the cosmic microwave background (CMB) and from the local cosmic distance ladder. Some analyses in the recent literature have shown intriguing hints for EDE. However, this model increases the tension in the derived clustering of galaxies (as measured by the so-calledS 8 parameter) between CMB and large scale structure (LSS) measurements. This new tension limits the contribution of EDE during recombination, and thus its effect on the Hubble tension. In this work, we investigate whether the inclusion of a general, smooth late-time dark energy modification can increase back the EDE contribution when LSS data is included in the analysis. In order to generalize the late expansion with respect to the ΛCDM model, we substitute the cosmological constant by a late dark energy fluid model with a piecewise constant equation of state w(z) in redshift bins. We show that, when analysing this generalized model with combinations of CMB, LSS and type Ia supernovae data from several experiments no significant changes onS 8 and EDE parameter constraints is found. The contribution to the EDE fraction constraint with late-time expansion marginalization isf EDE = 0.067 +0.019 -0.027 using 3 redshift bins, with similar results for 5 and 10 redshift bins. This work shows that in order to solve simultaneously the Hubble andS 8 tensions, one needs a mechanism for increasing the clustering of matter at late times different from a simple change in the background evolution of late dark energy.

Astronomy & Astrophysics↗
DOE OSTI2021

Singling out modified gravity parameters and data sets reveals a dichotomy between Planck and lensing

ABSTRACT An important route to testing general relativity (GR) at cosmological scales is usually done by constraining modified gravity (MG) parameters added to the Einstein perturbed equations. Most studies have analysed so far constraints on pairs of MG parameters, but here, we explore constraints on one parameter at a time while fixing the other at its GR value. This allows us to analyse various models while benefiting from a stronger constraining power from the data. We also explore which specific data sets are in tension with GR. We find that models with (μ = 1, η) and (μ, η = 1) exhibit a 3.9σ and 3.8σ departure from GR when using Planck18 + Supernovae type Ia (SNe) + Baryon acoustic oscillation (BAO), while (μ, η) shows a tension of 3.4σ. We find no tension with GR for models with the MG parameter Σ fixed to its GR value. Using a Bayesian model selection analysis, we find that some one-parameter MG models are moderately favoured over ΛCDM when using all data set combinations except Planck cosmic microwave background lensing and dark energy survey data. Namely, Planck18 shows a moderate tension with GR that only increases when adding any combination of redshift space distortion, SNe, or BAO. However, adding lensing diminishes or removes these tensions, which can be attributed to the ability of lensing in constraining the MG parameter Σ. The two overall groups of data sets are found to have a dichotomy when performing consistency tests with GR, which may be due to systematic effects, lack of constraining power, or modelling. These findings warrant further investigation using more precise data from ongoing and future surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Hubble constant difference between CMB lensing and BAO measurements

We apply a tension metric QUDM, the update difference in mean parameters, to understand the source of the difference in the measured Hubble constant H0 inferred with cosmic microwave background lensing measurements from the Planck satellite (H 0 = $67.9$ $^{+1.1}_{–1.3}$ km/s/Mpc) and from the South Pole Telescope (H 0 = $72.0$ $^{+2.1}_{–2.5}$ km/s/Mpc) when both are combined with baryon acoustic oscillation (BAO) measurements with priors on the baryon density (BBN). Q UDM isolates the relevant parameter directions for tension or concordance where the two data sets are both informative, and aids in the identification of subsets of data that source the observed tension. With Q UDM , we uncover that the difference in H 0 is driven by the tension between Planck lensing and BAO+BBN, at probability-to-exceed of 6.6%. Most of this mild tension comes from the galaxy BAO measurements parallel to the line of sight in the redshift range 0.2 < z < 0.75. Here, the redshift dependence of the parallel BAOs pulls both the matter density Ω m and H 0 high in Λ CDM, but these parameter anomalies are usually hidden when the BAO measurements are combined with other cosmological data sets with much stronger Ω m constraints.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Design and Analysis of a Floating-Wind Shallow-Water Mooring System Featuring Polymer Springs

This paper presents a mooring system design featuring polymer springs for the VolturnUS-S 15-MW reference floating wind turbine in site conditions for the New York Bight at a 50-m water depth. Polymer springs have a nonlinear stress-strain curve that allows a stiffer response at low loads and a more flexible response at higher loads, potentially reducing peak mooring line tensions. The mooring dynamics model MoorDyn has been extended to model springs with nonlinear tension-strain curves from a user-inputted look-up table. This MoorDyn modeling advancement is verified against OrcaFlex simulation results. Using MoorDyn's updated capabilities, a spring-equipped catenary mooring system is designed for the 15-MW floating system, along with a baseline catenary mooring system that does not use polymer springs. The floating wind turbine simulator OpenFAST is used to simulate the mooring systems in design-driving load cases to show the effect of polymer springs on key dynamic behaviours. The results show that the spring-equipped design reduces peak tensions by up to 60%, whereas the turbine offsets stay within a maximum of 7.2 m, which is still a reasonable offset limit for cable considerations. The reduction in peak tensions results in a significant decrease in damage equivalent loads - on the order of 50% for upwind lines in fully loaded conditions. These results show that polymer springs can effectively reduce peak tensions and fatigue loads in mooring systems at shallow water depths.

floating offshore wind↗
DOE OSTI2022

Design and Analysis of a Floating-Wind Shallow-Water Mooring System Featuring Polymer Springs: Preprint

In this paper, a mooring system featuring polymer springs is designed for the VolturnUS-S 15 MW reference floating wind turbine in site conditions for the New York Bight at a 50-m water depth. Polymer springs have a nonlinear stress-strain curve that allows a stiffer response at low loads and a more flexible response at higher loads, potentially reducing peak mooring line tensions. The mooring dynamics model MoorDyn has been extended to model springs with nonlinear tension-strain curves from a user-inputted look-up table. This MoorDyn modelling advancement is verified against OrcaFlex simulation results. Using MoorDyn's updated capabilities, a spring-equipped catenary mooring system is designed for the 15 MW floating system, along with a baseline catenary mooring system that does not use polymer springs. The floating wind turbine simulator OpenFAST is used to simulate the mooring systems in design-driving load cases to show the effect of polymer springs on key dynamic behaviours. The results show that the spring-equipped design reduces peak tensions by up to 60%, while the turbine offsets stay within a maximum of 7.2 m, which is still a reasonable offset limit for cable considerations. The reduction in peak tensions results in a significant decrease in damage equivalent loads, on the order of 50% for upwind lines in fully loaded conditions. These results show that polymer springs can effectively reduce peak tensions and fatigue loads in mooring systems at shallow water depths.

floating offshore wind↗
DOE OSTI2026

Adsorption of Mixed Micelles of Polysorbate 80 and Oleic Acid to the Air–Water Interface

The solubilization of long chain amphiphiles with limited solubility into mixed micelles composed of highly soluble surfactants plays a crucial role in modulating the stability and functionality of formulations in pharmaceutical and food systems. Subsequently, the mixed micelles adsorb from solution to the air−water surface, defining the transport mechanism of the insoluble amphiphiles to the interface. We use X-ray reflectivity to measure the composition and provide insight into the structure of these mixed monolayers, and, alongside interfacial tension measurements, we provide an understanding of how the bulk composition determines the surface composition and the dynamics of tension reduction. We use a model system consisting of an insoluble fatty acid, oleic acid (OA), and a soluble micelle-forming surfactant, polysorbate 80 (PS80). PS80 forms spherical micelles, and, above the critical micelle concentration (cmc), OA is readily solubilized inside the micelles. We show that the adsorption of PS80/OA mixed micelles to the air−water interface rapidly reduces the tension and lowers the equilibrium tension in proportion to the OA concentration. X-ray reflectivity data, fit using Parratt-slab models, quantitively demonstrates that the monolayers become enriched with OA, and we show how the OA intercalates into the PS80 monolayers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Failure in Confined Brazilian Tests on Sandstone

Strength of rocks in the confined tension region, where the minimum principal stress is tensile, has only infrequently been measured and is not well understood. Quasi-static confined Brazilian tests under a range of confining stresses (2.76 to 27.58 MPa) where used to determine the strength of sandstone in the confined tension region. The test results indicate that the strength in the confined tension region was a strong function of the intermediate principal stress: increasing the intermediate principal stress significantly increased the strength of the sandstone. The strength data were well fit by the Mogi–Coulomb criterion, which accounts for the intermediate principal stress. Unconfined Brazilian strength data were not well fit to the Mogi–Coulomb criterion derived from the confined Brazilian test data, consistent with a transition from tensile to shear processes dominating failure with increasing confining pressure. Observations of post-failure fracture surfaces reveal more indication of shear processes with increasing confining pressure. Numerical simulations from combined finite-discrete element method are compared to the experimental results and reflect similar conditions for failure compared to the experimental tests in the confined tension region.

42 ENGINEERING↗
DOE OSTI2020

Nonaxisymmetric Shapes of Biological Membranes from Locally Induced Curvature

In various biological processes such as endocytosis and caveolae formation, the cell membrane is locally deformed into curved morphologies. Previous models to study membrane morphologies resulting from locally induced curvature often only consider the possibility of axisymmetric shapes-an indeed unphysical constraint. Past studies predict that the cell membrane buds at low resting tensions and stalls at a flat pit at high resting tensions. In this work, we lift the restriction to axisymmetry to study all possible membrane morphologies. Only if the resting tension of the membrane is low, we reproduce axisymmetric membrane morphologies. When the resting tension is moderate to high, we show that 1) axisymmetric membrane pits are unstable and 2) nonaxisymmetric ridge-shaped structures are energetically favorable. Furthermore, we find the interplay between intramembrane viscous flow and the rate of induced curvature affects the membrane's ability to transition into nonaxisymmetric ridges and axisymmetric buds. In particular, we show that axisymmetric buds are favored when the induced curvature is rapidly increased, whereas nonaxisymmetric ridges are favored when the curvature is slowly increased. Overall, our results hold relevant implications for biological processes such as endocytosis and physical phenomena like phase separation in lipid bilayers.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Hydrodynamics of countercurrent flows in a structured packed column: effects of initial wetting and dynamic contact angle

The structured packed column has gained considerable attention as a prospective technology to mitigate carbon dioxide emissions from thermal power plants. The computational flow investigation of such systems is a multiscale problem, and local hydrodynamics plays a key role in overall column efficiency. Accordingly, multiphase flow studies in the representative elementary unit (REU) of a packed column can offer insights into the local flow behavior such as flow pattern, interfacial area, etc. The interfacial area plays a key role in the overall interphase mass transfer and thereby in separation efficiency. The predicted effective area matches well with corresponding ones in experiments for Mellapak 250.Y packings. The contact angle (i.e., solid substrate behavior) is one of the critical factors that dictates wettings, and thereby the interfacial area. The dynamic contact angle (DCA) was considered in order to explore the effects of contact angle hysteresis on the interfacial area. DCA has more pronounced impact on the interfacial area for a solvent possessing a higher value of surface tension and equilibrium contact angle. The interfacial area shows temporal undulation and does not achieve a pseudo steady state due to the capillary force. In contrary, the interfacial area gets a net value for a solvent having low surface tension value. Further, specification of the static contact angle at the solid substrate shows the least value of the interfacial area. We also extensively studied the effect of the initial sheet condition (dry vs wet) on the interfacial area. The initially wetted sheets show slightly higher value of the interfacial area as compared to the initially dry sheets at a fixed flow rate for a solvent having high surface tension value. Wetting hysteresis decreases with increasing liquid loads. On the other hand, wetting hysteresis does not occur for a solvent having value of low surface tension and equilibrium contact angle.

structured packings, dynamic contact angle, interf↗
DOE OSTI2021

Assessment of asymmetrical rheological behavior of cementitious material for 3D printing application

Among the multiplicity of construction methods based on digital concrete technologies, the most common one remains the extrusion-based process. Two opposed strategies have been developed in order to print a concrete structure using extrusion: the first one emphasizes the ease-of-pumping of material which is massively accelerated to ensure the stability of the structure, when leaving the extruder; the second one uses a firm mortar able to sustain the own weight of the structure during the printing, without requiring any accelerator. Both methods have their pros and cons and don't imply the same rheological requirements. Most of the recent literature assumes that both types of material (fluid and firm) follow the same trend of behavior and obey to the Von Mises plasticity criterion, while it has been demonstrated that firm cement-based materials can exhibit a pressure dependent behavior. Moreover, rheological study is mainly based on shear rheometry, while the extrusion-based printing process requires a description of the rheological behavior in compression to predict the global stability of the structure, and in tension to prevent cracks formation. This paper investigates the fresh behavior of cement paste and mortar under different solicitations (shear, compression, tension) for different water to cement ratios. The analysis of these results allows to describe the transition between a ductile fluid material (symmetrical in tension and compression) that obeys to a Von Mises plasticity criterion, and a brittle and firm material (asymmetrical in tension and compression) that requires a pressure dependent plasticity criterion in order to predict its strength under a given solicitation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanisms of paint bake response in resistance spot-welded first and third generation AHSS

Implementation of 3rd generation advanced high strength steels (3GAHSS) in automotive structures requires careful consideration of joining process implications. Due to the presence of increased carbon equivalent in 3GAHSS such as 980 HF relative to commonly-applied 1st generation AHSS such as 980 DP, the resultant properties of the weld nugget and heat affected zones in resistance spot welded must be engineered to provide consistent and acceptable performance, specifically in cross-tension loading mode. Although the as-welded cross-tension strength (CTS) of 980 HF is less than 980 DP, there is a significant improvement of the CTS after paint baking in 980 HF welds. 980 DP steel welds do not exhibit such marked improvement upon baking. The mechanism of the strong and beneficial effect of paint baking on 980 HF in comparison to 980 DP is discussed in light of its effect on residual stress distributions and microstructures. Although residual stress (strain) reduction is observed via synchrotron x-ray diffraction for all tested steels, this effect is demonstrated as secondary to the performance restoration of the weld joint in cross tension. High-resolution electron channeling contrast imaging (ECCI) micrographs reveal that paint baking affects a more beneficial degree of martensite tempering in 980 HF as compared to 980 DP. The martensite tempering is also evidenced by both a reduction in nano-hardness of critical microstructural features and re-emergence of ductile fracture behavior following the paint baking process. The tempering of martensite is concluded to be the dominant mechanism in improving cross tension strength of 3GAHSS welds following paint baking.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Foaming Dependence on the Interface Affinities of Surfactant-like Molecules

We have explored the relationship between physical properties and foaming behavior of 30 wt % aqueous monoethanolamine (MEA) solutions with three different surfactant-like additives. The additives included one commercial surfactant, cetyltrimethylammonium bromide (CTAB), and two CO 2 capture catalysts that behave as weak surfactants. The physical properties of interest were the additives’ affinity for the liquid–vapor interface and the viscosity, surface tension, and surface elasticity of the solutions. The physical properties were explored using molecular dynamics simulations as well as experiments. The additives’ affinity for the liquid–vapor interface played a key role in the foaming behavior by affecting the interfacial properties (surface tension and surface elasticity) of the aqueous MEA solutions. The solution containing CTAB showed the largest surface tension depression and the largest surface elasticity and resulted in the largest amount of foaming. The two catalyst solutions had almost similar surface tensions but differed in their elasticity. Here, the catalyst solution with higher surface elasticity showed more foaming due to higher foam stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Assembly of polyelectrolyte star block copolymers at the oil–water interface

To understand and resolve adsorption, reconfiguration, and equilibrium conformations of charged star copolymers, we carried out an integrated experimental and coarse-grained molecular dynamics simulation study of the assembly process at the oil–water interface. This is important to guide development of novel surfactants or amphiphiles for chemical transformations and separations. The star block copolymer consisted of arms that are comprised of hydrophilic–hydrophobic block copolymers that are covalently tethered via the hydrophobic blocks to one point. The hydrophobic core represents polystyrene (PS) chains, while the hydrophilic corona represents quaternized poly(2-vinylpyridine) (P2VP) chains. The P2VP is modeled to become protonated when in contact with an acidic aqueous phase, thereby massively increasing the hydrophilicity of this block, and changing the nature of the star at the oil–water interface. This results in a configurational change whereby the chains comprising the hydrophilic corona are significantly stretched into the aqueous phase, while the hydrophobic core remains solubilized in the oil phase. In the simulations, we followed the kinetics of the anchoring and assembly of the star block copolymer at the interface, monitoring the lateral assembly, and the subsequent reconfiguration of the star via changes in the interfacial tension that varies as the degree-of-protonation increases. At low fractions of protonation, the arm cannot fully partition into the aqueous side of the interface and instead interacts with other arms in the oil phase forming a network near the interface. These insights were used to interpret the non-monotonic dependence of pH with the asymptotic interfacial tension from pendant drop tensiometry experiments and spectral signatures of aromatic stretches seen in vibrational sum frequency generation (SFG) spectroscopy. We describe the relationship of interfacial tension to the star assembly via the Frumkin isotherm, which phenomenologically describes anti-cooperativity in adsorbing stars to the interface due to crowding. Although our model explicitly considers long-range electrostatics, the contribution of electrostatics to interfacial tension is small and brought about by strong counterion condensation at the interface. Finally, these results provide key insights into resolving the adsorption, reconfiguration, and equilibrium conformations of charged star block copolymers as surfactants.

36 MATERIALS SCIENCE↗